1. Field of the Invention
The present invention relates to a novel method of producing a catalyst useful in the reaction of ethylene, oxygen and acetic acid in the vapor phase to form vinyl acetate. In particular, the present invention is directed to a novel method of forming a catalyst useful in the catalytic formation of vinyl acetate in which said catalyst comprises metallic palladium and gold deposited on a suitable porous support.
2. Description of the Prior Art
It is known in the art that vinyl acetate can be produced by reacting ethylene, oxygen, and acetic acid in the gaseous phase and in the presence of a catalyst comprising palladium, gold and an alkali metal acetate supported on certain carrier materials such as silica. Generally, such catalyst system exhibits a high activity. Unfortunately, results utilizing such palladium and gold catalysts have been inconsistent. This inconsistency appears to be based somewhat on the distribution pattern or profile of the catalyst components which are deposited on and in relation to the support. For example, when use is made of the known vinyl acetate catalyst systems comprising a porous support with palladium and gold, the metal components deposited at or about the support interiors or central regions do not contribute significantly to the reaction mechanism, since the reactants are not readily able to diffuse into the central or inner regions of the porous network of the catalyst. Hence, the reaction occurs substantially only at the outermost or surface regions of the catalyst. The catalyst components in the interior regions of the support do not largely contribute to the reaction scheme, resulting in a reduction in catalytic efficiency per unit weight of the catalyst components. Furthermore, the use of a highly active catalyst at times gives rise to side reactions and, therefore, leads to a reduced selectivity to vinyl acetate.
Various patents have been granted based on the desire to more evenly distribute and anchor the gold and palladium catalytic components within a narrow band on the support surface to provide a vinyl acetate catalyst having high yield, good selectivity and long life. Examples of such patents include U.S. Pat. Nos. 4,087,622; 4,048,096; 3,822,308; 3,775,342 and British Patent 1,521,652.
The basic method of forming the vinyl acetate catalyst containing palladium and gold deposited on a catalyst support comprises (1) impregnating the support with aqueous solutions of water-soluble palladium and gold compounds, (2) precipitating water-insoluble palladium and gold compounds on the catalyst support by contacting the impregnated catalyst support with a solution of compounds capable of reacting with the water-soluble palladium and gold compounds to form the insoluble precious metal compounds (3) washing the treated catalyst with water to remove anions which are freed from the initially impregnated palladium and gold compounds during precipitation and (4) converting the water-insoluble palladium and gold compounds to the free metal by treatment with a reducing agent. A final treatment usually involves (5) impregnating the reduced catalyst with an aqueous alkali metal acetate solution and (6) drying the final catalyst product.
Prior art attempts to provide a uniform distribution of the palladium and gold metals on the support has involved some manipulation of the above mentioned steps and/or by using support materials having various specified pore dimensions.
It is an object of the present invention to provide a method of preparing a vinyl acetate catalyst which contains palladium and gold on a porous support in which the fixing of the water soluble precious metal compounds as water insoluble compounds on the support can be achieved by contacting the impregnated support with sufficient reactive compound to insure complete precipitation and fixing of the precious metal compounds onto the support in multiple fixing steps.